KR20200090815A - Stabilized, filled polycarbonate composition - Google Patents

Abstract

The present invention relates to the use of PMMI copolymers to reduce molecular weight reduction (derived by oxides such as titanium dioxide or silicon dioxide) of polymers in aromatic polycarbonate based compositions. Despite the addition of the PMMI copolymer, the mechanical, optical, and rheological properties of the thermoplastic composition remain excellent, even improving in some cases.

Description

Stabilized, filled polycarbonate composition

The present invention is aromatic in polycarbonate compositions filled with oxides of metals or quaternary metals of the third or fourth major or fourth transition group for molecular weight decomposition, with the least possible impact on mechanical properties, especially heat resistance. Stabilization of polycarbonates, and thus the use of novel additives for this purpose, and aromatic polycarbonates and at least one oxide of metals or metalloids of the third or fourth main or fourth transition group The corresponding composition, and thus also relates to a method for preventing/reducing polycarbonate decomposition by addition of such an oxide. The present invention also relates to moldings made from these compositions.

The production of a filled polycarbonate composition by blending, depending on the filler, results in the molecular weight decomposition of the polycarbonate under process conditions customary for the material. Fillers, especially those having reactive groups on the surface, can be subjected to a chemical reaction with polycarbonate. These reactions can lead to chain cleavage and hence molecular weight degradation. This problem is described in particular in US 2006/0287422 A1.

In addition, molecular weight degradation adversely affects the optical, rheological, mechanical and thermal properties of the polycarbonate composition. Therefore, it is essential to add to the composition a process stabilizer that inhibits the degradation of the polymer chains, i.e. the molecular weight degradation.

For the stabilization of polycarbonates, there have been extensively studied additives to date, based on the antioxidant effect of organic phosphorus compounds. Thus, for example, in WO 2011/038842 A1 it is described that the addition of a small amount of phosphate can improve the melt stability and thus the molecular weight degradation during processing of the polycarbonate composition. Related yellowing and thus degradation of optical properties is also minimized. DE 102009043513 A1 describes combinations of different organophosphorus compounds to improve the optical properties of polycarbonate compositions. However, since the working principle is based on the redox method, effective stabilization of the filler-based polycarbonate compound cannot be realized.

From a modern point of view, there are two types of additives (e.g. inorganic acids described in WO 2013/060687 A1, for example phosphoric acid or phosphorous acid), which are capable of counteracting this type of polymer degradation. Also present are organic acids (typically carboxylic acids), for example described in DE 102005058847 A1, for example citric acid or acid-functionalized olefinic (co)polymers. However, the use of such systems in polycarbonate compositions is associated with disadvantages. When added in excess, the high acidity of the inorganic acid can itself lead to splitting of the carbonate units and hence decomposition. Organic acids typically decompose well below the typical processing temperature of polycarbonate (260-400°C). Thus, for example, citric acid decomposes from 175°C. However, considering their relatively low viscosity, typical polymer or oligomer systems based on olefinic bases having carboxylic acid or carboxylic anhydride functionalities above certain critical concentrations have been used to plasticize polycarbonate and to This results in a partial loss of mechanical and thermal properties.

For the reasons mentioned above, it does not decompose under the processing conditions of the polycarbonate, does not negatively impair the mechanical and thermal properties of the polycarbonate, and ideally finds additives with sufficient stabilizing action, even at low concentrations It is preferred.

Conventional process stabilizers such as phosphite or phosphonite have been shown to be unsuitable for suppression of filler-induced degradation. In filled thermoplastics, in particular, oxidized, acid-modified polyolefin-based (co)polymers, for example HiWax from Mitsui Chemicals, or AC products from Honeywell Is used. WO 2016/087477 A1 describes the use of oxidized polyethylene wax in polycarbonate and its effect on heat resistance, among other properties. These additives, due to their low melting point, can negatively affect thermal and mechanical properties, even in small amounts. Depending on the filler content, stabilization of the filled polycarbonate composition requires a wax concentration >1% by weight. However, at higher concentrations, these additives have a plasticizing effect, thus reducing the reinforcing effect of the filler and thus its main purpose. Additionally, the miscibility of these olefinic waxes and polycarbonates decreases rapidly with increasing content, thus leading to marked turbidity of the compounds. In addition, in the case of the addition of fillers, this also adversely affects the colorability and results in a delamination effect on the surface of the material. In addition, these waxes are unstable under extended thermal stress, which results in faster yellowing of the material.

Thus, the problem addressed is a novel novel stabilizer suitable for inhibiting the molecular weight degradation of aromatic polycarbonates in metal/metalloid oxide-filled polycarbonate compositions without adversely affecting the actual reinforcing effect of the filler. It was a matter of identification of, and provision of a corresponding composition. Compared to compositions without new stabilizers, even if present in the thermal, mechanical, optical and rheological properties of the polycarbonate composition, it should have very little negative impact.

Surprisingly, this problem is solved by the addition of PMMI copolymer to the polycarbonate composition. Addition of PMMI copolymers substantially improves the heat resistance and mechanical and rheological properties of the polycarbonate compositions, in some cases, in fact.

Thus, the present invention is in a polycarbonate composition filled with at least one oxide of a metal or metalloid of a third or fourth main group or a fourth transition group, during blending, particularly also during blending using a co-kneader. Provides the use of PMMI copolymers to suppress, ie at least reduce, preferably avoid molecular weight degradation of aromatic polycarbonates. Co-kneaders typically have a relatively high residence time, so good stabilization is of particular importance here.

The formulation is a mixture of additives, especially fillers and additives, to the polymer, here aromatic polycarbonate. This is typically achieved by an extruder, also at temperatures in the extruder above 260°C.

Therefore, the present invention also

A) aromatic polycarbonate,

B) at least one oxide of a metal or metalloid of the third or fourth main or fourth transition group, in particular titanium dioxide, silicon dioxide and/or aluminum oxide,

C) PMMI copolymer and

D) optionally additional additives

It provides a composition containing a.

The term "at least one oxide of a metal or metalloid of a third or fourth major group or a fourth transition group" is one or more oxides of a metal or metalloid of a third major group, a fourth major group and/or a fourth transition group" Is synonymous with.

The individual components are described in detail below.

Component A

Component A of the composition is selected from aromatic polycarbonates.

Aromatic polycarbonates in the context of the present invention include homopolycarbonates as well as copolycarbonates and/or polyestercarbonates; The polycarbonate can be linear or branched in a known manner. According to the invention, mixtures of polycarbonates may be used.

Thermoplastic polycarbonates, including thermoplastic aromatic polyestercarbonates, are preferably linear polycarbohydrates with a known molar mass distribution from PSS Polymer Standards Service GmbH (Germany). Correction with Nate (formed from bisphenol A and phosgene), and Kurenta Gembhaunt Co. Calibration by method 2301-0257502-09D (2009, German version) from Ohren (Currenta GmbH & Co. OHG, Leverkusen, Germany), calibration against bisphenol A polycarbonate standards using dichloromethane as eluent Weight-average of 15,000 to 40,000 g/mol, more preferably 34,000 g/mol, particularly preferably 17,000 to 33,000 g/mol, particularly 19,000 to 32,000 g/mol, measured by gel permeation chromatography It has a molecular weight M _w . The eluent is dichloromethane. Column combination of crosslinked styrene-divinylbenzene resin. Diameter of the analytical column: 7.5 mm; Length: 300 mm. The particle size of the column material: 3 μm to 20 μm. Concentration of solution: 0.2% by weight. Flow rate: 1.0 ml/min, solution temperature: 30°C. Use of UV and/or RI detection.

Portions of up to 80 mol% of the carbonate groups in the polycarbonate used according to the invention, preferably from 20 mol% to 50 mol%, may be replaced by aromatic dicarboxylic acid ester groups. Such polycarbonates containing both acid radicals of carbonic acid and aromatic dicarboxylic acids incorporated in molecular chains are referred to as aromatic polyestercarbonates. For the purposes of the present invention, they are included in the generic term "thermoplastic aromatic polycarbonate".

Polycarbonates are prepared in a known manner from dihydroxyaryl compounds, carbonic acid derivatives, optionally chain terminators, and optionally branching agents, and polyestercarbonates are used to form part of the carbonic acid derivatives, aromatic dicarboxylic acids or dicarboxylic acids. It is prepared by substituting a derivative of an carboxylic acid, and specifically, depending on the degree to which a carbonate structural unit in an aromatic polycarbonate should be replaced with an aromatic dicarboxylic ester structural unit.

Dihydroxyaryl compounds suitable for the production of polycarbonates are those of formula (1):

here,

Z is an aromatic radical having 6 to 30 carbon atoms, may contain one or more aromatic rings, may be substituted, and may contain an aliphatic or cycloaliphatic radical or alkylaryl or heteroatom as a bridging element.

It is preferred that Z in formula (1) represents a radical of formula (2):

here,

R ⁶ and R ⁷ are independently of each other H, C ₁ -to C ₁₈ -alkyl, C ₁ -to C ₁₈ -alkoxy, halogen, such as Cl or Br, or optionally substituted aryl or aralkyl in each case, preferably Represents H or C ₁ -to C ₁₂ -alkyl, particularly preferably H or C ₁ -to C ₈ -alkyl, also very particularly preferably H or methyl,

X is a single bond, -SO ₂ -, -CO-, -O-, -S-, C ₁ -to C ₆ -alkylene, C ₂ -to C ₅ -alkylidene or C ₅ -to C ₆ -cyclo alkylidene (which is C ₁ - to C ₆ - alkyl, preferably may be substituted by methyl or ethyl) to indicate or, in the more containing a hetero atom may be optionally fused to an aromatic ring C ₆ - to C ₁₂ -arylene.

X is a single bond, C ₁ -to C ₅ -alkylene, C ₂ -to C ₅ -alkylidene, C ₅ -to C ₆ -cycloalkylidene, -O-, -SO-, -CO-, -S -, -SO _2-

Or it is preferred to represent radicals of formula (3):

.

.

Examples of the dihydroxyaryl compound (diphenol) include dihydroxybenzene, dihydroxydiphenyl, bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloalkane, bis(hydroxyphenyl)aryl, bis (Hydroxyphenyl) ether, bis(hydroxyphenyl) ketone, bis(hydroxyphenyl) sulfide, bis(hydroxyphenyl) sulfone, bis(hydroxyphenyl) sulfoxide, 1,1'-bis(hydroxy Phenyl)diisopropylbenzene and their ring-alkylated and ring-halogenated compounds.

Dihydroxyaryl compounds suitable for the production of polycarbonates and copolycarbonates for use in accordance with the present invention include, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenyl)alkanes, Bis(hydroxyphenyl)cycloalkane, bis(hydroxyphenyl) sulfide, bis(hydroxyphenyl) ether, bis(hydroxyphenyl) ketone, bis(hydroxyphenyl) sulfone, bis(hydroxyphenyl) sulfoxide , α,α'-bis(hydroxyphenyl)diisopropylbenzene, and alkylated, ring-alkylated and ring-halogenated compounds thereof. Copolycarbonates can also be made using Si-containing telechelics to obtain so-called Si-copolycarbonates.

Preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(4-hydroxyphenyl)phenylethane , 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(4-hydroxyphenyl)-2 -Propyl]benzene (bisphenol M), 2,2-bis(3-methyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3 ,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2- Methylbutane, 1,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene and 1,1-bis(4-hydroxyphenyl)-3,3,5- Trimethylcyclohexane (bisphenol TMC), and also bisphenols of formulas (I) to (III):

Here, R'in each case represents a C ₁ -C ₄ -alkyl radical, an aralkyl radical or an aryl radical, preferably a methyl radical or a phenyl radical, most preferably a methyl radical.

Particularly preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2, 2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane and 1,1-bis(4-hydroxyphenyl)-3,3, 5-trimethylcyclohexane (bisphenol TMC), and also dihydroxyaryl compounds of formulas (I), (II) and/or (III).

These and further suitable dihydroxyaryl compounds are, for example, US 2 999 835 A, 3 148 172 A, 2 991 273 A, 3 271 367 A, 4 982 014 A and 2 999 846 A, German published specification 1 570 703 A, 2 063 050 A, 2 036 052 A, 2 211 956 A and 3 832 396 A, French patent specification 1 561 518 A1, thesis [H. Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York 1964, pp. 28ff and pp. 102ff.], and [D.G. Legrand, J.T. Bendler, "Handbook of Polycarbonate Science and Technology", Marcel Dekker New York 2000, pp. 72ff].

In the case of homopolycarbonate, only one dihydroxyaryl compound is used; In the case of copolycarbonates, two or more dihydroxyaryl compounds are used.

Particularly preferred polycarbonates are bisphenol A based homopolycarbonates, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane based homopolycarbonates and two monomer bisphenols. A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane or two monomers bisphenol A and 4,4'-dihydroxydiphenyl based copolycarbonate, and formula It is a homo- or copolycarbonate (especially having bisphenol A) derived from the dihydroxyaryl compounds of (I), (II) and/or (III):

Here, R'in each case represents C ₁ -C ₄ -alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl.

The dihydroxyaryl compounds used, like all other chemicals and auxiliaries added to synthesis, can be contaminated with impurities derived from their own synthesis, handling and storage. However, it is preferable to use a raw material with high purity as much as possible.

Also preferred are copolycarbonates having one or more monomer units of the siloxane of general formula (IV):

here,

R ¹⁹ represents hydrogen, Cl, Br or a C ₁ -to C ₄ -alkyl radical, preferably hydrogen or a methyl radical, particularly preferably hydrogen,

R ¹⁷ and R ¹⁸ are the same or different and independently of each other represent an aryl radical, a C ₁ -C ₁₀ -alkyl radical or a C ₁ -C ₁₀ -alkylaryl radical, preferably in each case a methyl radical, wherein

X is a single bond, -CO-, -O-, C ₁ -to C ₆ -alkylene radical, C ₂ -to C ₅ -alkylidene radical, C ₅ -to C ₁₂ -cycloalkylidene radical or C _6- To C ₁₂ -arylene radicals (which may optionally be condensed with additional aromatic rings containing heteroatoms), wherein X is preferably a single bond, a C ₁ -to C ₅ -alkylene radical, C _2- To C ₅ -alkylidene radicals, C ₅ -to C ₁₂ -cycloalkylidene radicals, -O- or -CO-, more preferably single bonds, isopropylidene radicals, C ₅ -to C ₁₂ -cycloalkylidene A radical or -O-, very particularly preferably an isopropylidene radical,

n is a number from 1 to 500, preferably from 10 to 400, particularly preferably from 10 to 100, very particularly preferably from 20 to 60,

m is a number from 1 to 10, preferably from 1 to 6, particularly preferably from 2 to 5,

p is 0 or 1, preferably 1

The value of the product of n and m is preferably 12 to 400, more preferably 15 to 200,

Here the siloxane is preferably reacted with a polycarbonate in the presence of an organic or inorganic salt of a weak acid with a pK _A of 3 to 7 (25° C.).

Copolycarbonates having monomeric units of formula (IV) and especially also their preparation are described in WO 2015/052106 A2.

The total proportion of monomer units based on the formulas (I), (II), (III), 4,4'-dihydroxydiphenyl and/or bisphenol TMC in the copolycarbonate is preferably 0.1-88 mol% , Particularly preferably 1-86 mol%, very particularly preferably 5-84 mol%, and also particularly 10-82 mol% (based on the sum of the number of moles of dihydroxyaryl compound used).

Copolycarbonates can be in the form of block copolycarbonates and random copolycarbonates. Random copolycarbonates are particularly preferred.

The ratio of the frequency of diphenoxide monomer units in the copolycarbonate is derived from the molar ratio of dihydroxyaryl compounds used herein.

The relative solution viscosity of the copolycarbonate, measured according to ISO 1628-4:1999, is preferably in the range of 1.15-1.35.

Monofunctional chain terminators required for molecular weight control, such as phenol or alkylphenols, especially phenols, p-tert-butylphenols, isooctylphenols, cumylphenols, acid chlorides of their chlorocarbonate esters or monocarboxylic acids or these chain species The mixture of the settlement is fed to the reaction with the bisphenoxide(s), or added to the synthesis at any time, provided that the phosgene or chlorocarbonate end groups are still present in the reaction mixture, or acid chloride as chain terminator And in the case of chlorocarbonate esters, provided that sufficient phenolic end groups of the initial polymer are available. However, it is preferred that the chain terminator(s) is added at a position or time point when phosgene is no longer present after phosgenation, but the catalyst has not yet been added, or they are added before or with or in combination with the catalyst. Do.

Any branching agent or branching agent mixture used is added to the synthesis in the same way, but typically before the chain terminator. Typical compounds used are trisphenol, quarterphenol or acyl chloride of tri- or tetracarboxylic acids, or mixtures of polyphenols or acyl chloride.

Some of the compounds having three or more than three phenolic hydroxyl groups usable as branching agents are, for example, fluoroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxy Phenyl)hept-2-ene, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1, 1-tri(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4- Bis(4-hydroxyphenylisopropyl)phenol, tetra(4-hydroxyphenyl)methane.

Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-di It is hydroindole.

Preferred branching agents are 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole and 1,1,1-tri(4-hydroxyphenyl)ethane.

The amount of branching agent for optional use is also 0.05 mol% to 2 mol%, based on the number of moles of diphenol used in each case.

The branching agent may be initially charged with diphenols and chain terminators in an aqueous alkali phase, or it may be added dissolved in an organic solvent prior to phosgenation.

All of these measures for the production of polycarbonate are familiar to those skilled in the art.

Aromatic dicarboxylic acids suitable for the production of polyester carbonates are, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'- Diphenyl dicarboxylic acid, 4,4-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl Sulfone dicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, trimethyl-3-phenylindan-4,5'-dicarboxylic acid.

Among aromatic dicarboxylic acids, it is particularly preferable to use terephthalic acid and/or isophthalic acid.

Derivatives of dicarboxylic acids include dicarbonyl dihalides and dialkyl dicarboxylates, especially dicarbonyl chloride and dimethyl dicarboxylate.

The replacement of the carbonate group with an aromatic dicarboxylic acid ester group proceeds essentially stoichiometrically and also quantitatively, so that the molar ratio of the reaction partners also appears in the final polyestercarbonate. Aromatic dicarboxylic acid ester groups can be incorporated randomly or in a block fashion.

Preferred methods of preparing polycarbonates used according to the invention, including polyester carbonates, are known interface methods and known melt transesterification methods (for example WO 2004/063249 A1, WO 2001/05866 A1, US 5,340,905 A, US 5,097,002 A, US-A 5,717,057 A).

In the former case, the acid derivative used is preferably phosgene and optionally dicarbonyl dichloride; In the latter case, these are preferably diphenyl carbonates and optionally dicarboxylic acid diesters. Catalysts, solvents, workups, reaction conditions, etc. for polycarbonate production/polyestercarbonate production are fully described and known in both cases.

The composition in the context of the present invention is preferably a "polycarbonate composition" or "polycarbonate based composition". These are base materials, ie compositions in which the dominant component present is polycarbonate. “Dominant” herein, based on the total composition, is at least 55% by weight, preferably at least 60% by weight, more preferably at least 68% by weight, and even more preferably at least 70% by weight, particularly preferably at least It is understood to mean 74% by weight of aromatic polycarbonate.

Component B

The composition according to the invention contains as component B at least one oxide of a metal or metalloid of the third or fourth main or fourth transition group. Oxides of metals or metalloids of the third or fourth main group or the fourth transition group may be used alone or in mixtures. Components preferably based on titanium dioxide, silicon dioxide and/or silicon dioxide, such as glass fibers, and/or aluminum oxide, particularly preferably titanium dioxide and/or silicon dioxide, very particularly preferably titanium dioxide, in particular Used without additional oxides of metals or metalloids of the third or fourth main or fourth transition group (except for titanium dioxide and/or silicon dioxide coatings).

Component B, in each case based on the total composition, is preferably 5% to 44% by weight, more preferably 5% to 40% by weight, and more preferably 8% to 32% by weight , Particularly preferably in an amount of 10% to 30% by weight, very particularly preferably in an amount of 15% to 25% by weight in the composition according to the invention.

Silicon dioxide is preferably natural or synthetically produced quartz or fused quartz.

The quartz used in the composition according to the invention preferably has a spherical and/or approximately spherical granular shape. Approximately spherical is understood to have the following meaning: If the sphere is described by an equal-length axis that runs from a common origin and is oriented into the space (where the axis defines the radius of the sphere in all spatial directions), the spherical particle is It can also have an axial length deviation from the ideal state for a sphere of 20% or less to qualify as approximately spherical.

Quartz is preferably characterized by a median diameter d ₅₀ measured according to ISO 13320:2009 of 2 to 10 μm, more preferably 2.5 to 8.0 μm, and more preferably 3 to 5 μm, here 6 to Preference is given to a maximum diameter d ₉₅ measured according to ISO 13320:2009 of 34 μm, more preferably 6.5 to 25.0 μm, more preferably 7 to 15 μm, and particularly preferably 10 μm.

Quartz is preferably BET specific surface area measured by nitrogen adsorption according to ISO 9277:2010 of 0.4 to 8.0 m 2 /g, more preferably 2 to 6 m 2 /g, and also particularly preferably 4.4 to 5.0 m 2 /g Have

More preferred quartz contains only 3% by weight or less of the secondary constituent, wherein preferably, in each case based on the total weight of quartz/silicate,

The content of Al ₂ O ₃ is <2.0% by weight,

The content of Fe ₂ O ₃ is <0.05% by weight,

The content of (CaO + MgO) is <0.1% by weight,

The content of (Na ₂ O + K ₂ O) is <0.1% by weight

to be.

It is preferred to use quartz with a pH measured according to ISO 10390:2005 in aqueous suspensions ranging from 6 to 9, more preferably from 6.5 to 8.0.

Preferably said quartz has an oil absorption value according to DIN EN ISO 787-5:1995-10, preferably from 20 to 30 g/100 g.

In a preferred embodiment component B is a finely divided quartz powder produced by iron free milling followed by air sieving from the post-treated quartz sand.

Particular preference is given to using fused silica, ie fused quartz, which is fused and reconsolidated silicon dioxide, as component B.

Quartz or quartz glass having a size on its surface can be used and include epoxy-modified, polyurethane-modified and unmodified silane compounds, methylsiloxane and methacryloylsilane sizes, or mixtures of the silane compounds mentioned above. It is preferred to use. Epoxysilane size is particularly preferred. Sizing of silicon dioxide is carried out by general methods known to those skilled in the art.

However, it is preferred that the silicon dioxide used in the composition according to the invention is not sized.

Suitable titanium dioxide is preferably those which are suitable for use in hydrophobized, special post-treated and polycarbonate prepared by the chloride process, for example the commercially available product Kronos 2230 (Kronos It is Kronos Titan.

Possible surface modifications of titanium dioxide include inorganic and organic modifications. These include, for example, surface modification based on aluminum or polysiloxanes. The inorganic coating may contain 0% to 5% by weight of silicon dioxide and/or aluminum oxide. Modification of the organic substrate may contain 0% to 3% by weight of a hydrophobic wetting agent.

Titanium dioxide is preferably 12 to 18 g/titanium dioxide 100 g, more preferably 13 to 17 g/titanium dioxide 100 g, particularly preferably 13.5 to 15.5 g/titanium dioxide 100 g, DIN EN ISO 787 -5: has an oil absorption value measured according to 1995-10.

Particular preference is given to titanium dioxide with the standard designation R2 according to DIN EN ISO 591, part 1, stabilized with aluminum and/or silicon compounds and having a titanium dioxide content of at least 96.0% by weight. Such titanium dioxide is available under the trade names Kronos® 2233 and Kronos® 2230.

When aluminum oxide is used as component B, it preferably has a pH of 7.0 to 7.4 measured according to ISO 10390:2005 in aqueous suspension. It is preferably not sized.

The amount specified for component B in each case is for the total weight of oxide used, including any size/surface modification.

Component C

Component C is selected from PMMI copolymers. These are thermoplastics that are partially imidized methacrylic polymers. PMMI copolymers are obtained, in particular, by the reaction of methylamine and PMMA in a dispersion or melt in a reactor. Suitable methods are described, for example, in DE 1 077 872 A1. The imide structure is produced along the polymer chain, depending on the degree of reaction and also with the formation of methacrylic anhydride and free methacrylic acid functional groups. The proportion of imide functional groups in the copolymer determines its heat resistance. The degree of reaction is specifically adjustable.

PMMI copolymers have methyl methacrylate (MMA, 4a), methylmethacrylimide (MMI, 6), methylmethacrylic acid (MMS, 4b) and methylmethacrylic anhydride units (MMAH, 5). Based on the total weight of the PMMI copolymer, preferably at least 90% by weight, more preferably at least 95% by weight of the PMMI copolymer is selected from MMA, MMI, MMS and MMAH units. It is particularly preferred that the PMMI copolymer consists of these units.

MMA: 4a (R=R'=CH ₃ ), MMS: 4b (R=CH ₃ , R'=H), MMAH: 5 (R=CH ₃ ), MMI: 6 (R=R'=CH ₃ ) .

The ratios of units and PMMI copolymers can be determined by quantitative ¹ H NMR spectroscopy, in particular based on the clear chemical shift of the R'signal. Signals of acid and anhydride monomer units cannot be assigned clearly, and therefore, overall consideration of these units is desirable.

The PMMI copolymer is preferably at least 30% by weight, preferably at least 35% by weight, more preferably 35% to 96% by weight, particularly preferably 36% by weight, based on the total weight of the PMMI copolymer. It has an MMI ratio of MMI of% to 95% by weight.

The MMA ratio of the copolymer is preferably 3% to 65% by weight, preferably 4% to 60% by weight, particularly preferably 4.0% to 55% by weight, based on the total weight of the PMMI copolymer. %to be.

The total ratio of MMS and MMAH is preferably 15% by weight or less, more preferably 12% by weight or less, particularly preferably 0.5% by weight to 12% by weight, based on the total weight of the PMMI copolymer.

The acid value of the PMMI copolymer, measured according to DIN 53240-1:2013-06, is preferably 15 to 50 mg KOH/g, more preferably 20 to 45 mg KOH/g, also more preferably 22 to 42 mg KOH/g.

Very particularly preferred PMMI copolymers, as measured by ¹ H NMR spectroscopy, based on the total weight of the PMMI copolymer in each case, have an MMI ratio of 36.8 wt%, an MMA ratio of 51.7 wt% and an MMS of 11.5 wt% It has a +MMAH ratio, and an acid value of 22.5 mg KOH/g measured according to DIN 53240-1:2013-06.

Alternatively, very particularly preferred PMMI copolymers have an MMI ratio of 83.1% by weight, an MMA ratio of 13.6% by weight and 3.3% by weight based on the total weight of the PMMI copolymer in each case, as determined by ¹ H NMR spectroscopy. % MMS+MMAH ratio, and acid value of 22.5 mg KOH/g, measured according to DIN 53240-1:2013-06.

Also alternatively very particularly preferred PMMI copolymers, as measured by ¹ H NMR spectroscopy, based on the total weight of the PMMI copolymer in each case, have an MMI ratio of 94.8 wt%, an MMA ratio of 4.6 wt% and 0.6 It has an MMS+MMAH ratio in weight percent, and an acid value of 41.5 mg KOH/g measured according to DIN 53240-1:2013-06.

Suitable PMMIs are available, for example, from the Evonik Industries AG under the “PLEXIMID®” brand.

In polycarbonate compositions containing oxides of metals or metalloids of the third or fourth major or fourth transition group, the amount added to the PMMI copolymer is based on the total weight of the polycarbonate composition in each case. Thus, preferably at least 1% by weight, more preferably at least 1.5% by weight, more preferably at least 2% by weight, also more preferably at least 3% by weight, particularly preferably 4% by weight, very particularly preferred It is less than or equal to 6% by weight.

It is preferred that the ratio of component B to PMMI copolymer is ≦40, more preferably ≦30, and even more preferably ≦25, especially ≦20.

The glass transition temperature of the PMMI copolymer measured according to DIN EN ISO 11357-2:2014-07 at a heating rate of 20°C/min is preferably 130°C to 170°C. Therefore, PMMI copolymers are stable under the processing conditions typical for polycarbonates, including hot-stable polycarbonate copolymers.

Component D

Compositions according to the invention may contain one or more additional additives separate from component B and component C, which are summarized herein as “component D”.

The additive is optionally (0% by weight) in the composition according to the invention, preferably up to 20.0% by weight, more preferably up to 10.0% by weight, more preferably 0.10% to 8.0% by weight, particularly preferably 0.2 It is present in an amount of from weight percent to 3.0 weight percent, where these weight percentages are based on the total weight of the composition.

Additives typically added to polycarbonates are, for example, EP 0 839 623 A1, WO 96/15102 A2, EP 0 500 496 A1 or the "Plastics Additives Handbook", Hans Zweifel, 5th Edition 2000, Hanser Verlag , Munich. Suitable additives are in particular flame retardants, anti-dropping agents, impact modifiers, fillers, antistatic agents, organic and inorganic colorants such as pigments and carbon blacks, lubricants and/or release agents, heat stabilizers, blend partners, such as ABS, polyesters such as PET and/or PBT, or SAN, compatibilizers, UV absorbers and/or IR absorbers.

Preferred mold release agents are esters of aliphatic long chain carboxylic acids with monovalent or polyvalent aliphatic and/or aromatic hydroxyl compounds. Particular preference is given to pentaerythritol tetrastearate, glycerol monostearate, stearyl stearate and propanediol distearate or mixtures thereof.

Preferred UV stabilizers have the lowest possible transmission of less than 400 nm and the highest possible transmission of greater than 400 nm. UV absorbers particularly suitable for use in the composition according to the invention are benzotriazole, triazine, benzophenone and/or arylated cyanoacrylate.

Particularly suitable ultraviolet absorbers are hydroxybenzotriazoles such as 2-(3',5'-bis(1,1-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole (Tinuvin® 234, Ciba Spezialitaetenchemie (Basel, Switzerland), 2-(2'-hydroxy-5'-(tert-octyl)phenyl)benzotriazole (Tinuvin® 329, Ciba Spezialitatenkemi, Switzerland Basel), 2-(2'-hydroxy-3'-(2-butyl)-5'-(tert-butyl)phenyl)benzotriazole (Tinuvin® 350, Ciba spezialitanatechemy, Basel, Switzerland) , Bis(3-(2H-benzotriazolyl)-2-hydroxy-5-tert-octyl)methane (Tinuvin® 360, Ciba Spezialitaetenchemy, Basel, Switzerland), (2-(4,6- Diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol (Tinuvin® 1577, Ciba spegalitaetensemi, Basel, Switzerland), and benzophenone 2,4-di Hydroxybenzophenones (Chimassorb® 22, Ciba spegalitaetensemi, Basel, Switzerland) and 2-hydroxy-4-(octyloxy)benzophenones (Cimasorb® 81, Ciba, Basel, Switzerland) , 2-cyano-3,3-diphenyl-2-propenoic acid 2-ethylhexyl ester, 2,2-bis[[(2-cyano-1-oxo-3,3-diphenyl-2- Propenyl)oxy]methyl]-1,3-propanediyl ester (9CI) (Uvinul® 3030, BASF AG, Ludwigshafen, Germany)), 2-[2-hydroxy-4-( 2-ethylhexyl)oxy]phenyl-4,6-di(4-phenyl)phenyl-1,3,5-triazine (CGX UVA 006, Ciba spegalitaetensemi, Basel, Switzerland) or tetraethyl 2,2 '-(1,4-phenylenedimethylidene) bismalonate (Hostavin® B-Cap, Clariant AG).

Particularly preferred specific UV stabilizers are, for example, Tinuvin® 360, Tinuvin® 350, Tinuvin® 329, Hostavin® B-CAP, more preferably TIN 329 and Hostavin® B-Cap. It is also possible to use mixtures of these ultraviolet absorbers.

When a UV absorber is present, the composition preferably comprises an ultraviolet absorber, based on the total composition, from 0 ppm to 6000 ppm, more preferably from 500 ppm to 5000 ppm, even more preferably from 1000 ppm to 2000 ppm. Contains in quantity.

Suitable IR absorbers are disclosed, for example, in EP 1 559 743 A1, EP 1 865 027 A1, DE 10022037 A1, DE 10006208 A1 and Italian patent applications RM2010A000225, RM2010A000227 and RM2010A000228. Of the IR absorbers mentioned in the cited references, boride and tungstate based ones are preferred, especially cesium tungstate or zinc-doped cesium tungstate, and also ITO- and ATO based absorbers and combinations thereof.

Suitable colorants can be pigments, organic and inorganic pigments, carbon black and/or dyes. Colorants or pigments separate from component B in the context of the present invention are sulfur-containing pigments, such as cadmium red or cadmium yellow, pigments based on iron cyanide, such as Prussian blue, oxide pigments, such as zinc oxide, red iron oxide , Black iron oxide, chromium oxide, titanium yellow, zinc/iron based brown, titanium/cobalt based green, cobalt blue, copper/chromium based black and copper/iron based black or chromium based pigments such as chromium yellow, Phthalocyanine-derived dyes such as copper phthalocyanine blue or copper phthalocyanine green, fused polycyclic dyes and pigments such as azo based ones (eg nickel azo yellow), sulfur indigo dyes, perinone based, perylene based, quina It is a dioxone-based, isoindolinone-based and quinophthalone-derived derivative, anthraquinone-based heterocyclic system derived from cridon. However, the colorant of component D does not particularly contain titanium dioxide, since it is included in component B.

Specific examples of commercial products are, for example, Macrolex® Blue RR, Macrolex® Violet 3R, Macrolex® Violet B (Lanxess AG, Germany), Sumiplast® Violet RR, Sumiplast® Violet B, Sumiplast® Blue OR (Sumitomo Chemical Co., Ltd.), Diaresin® Violet D, Diaresine® Blue G, Dia Lesin® Blue N (Mitsubishi Chemical Corporation), Heliogen® Blue or Heliogen® Green (BASF AG, Germany). Of these, cyanine derivatives, quinoline derivatives, anthraquinone derivatives, and phthalocyanine derivatives are preferred.

Fillers other than component B may also be added provided that they do not compromise the performance level of the present invention depending on their nature and amount. These can have, for example, particulate, flaky or fibrous characteristics. Examples include chalk, barium sulfate, silicate/aluminosilicates such as wollastonite, mica/clay foliar minerals, montmorillonite (especially also in the form of organic affinity modified by ion exchange), kaolin, zeolite, vermiculite, carbon fiber, Magnesium hydroxide and aluminum hydroxide. It is also possible to use mixtures of different inorganic materials.

In addition, depending on the nature of the ingredients and their amount, additional ingredients that do not impair the performance level of the present invention can be added.

Preferred compositions according to the invention

A) at least 55% by weight of aromatic polycarbonate,

B) from 5% to 44% by weight of one or more oxides of metals or metalloids of the third, fourth, and/or fourth transition group,

C) 0.1% to 8% by weight of PMMI copolymer and

D) optionally additional additives

It contains.

More preferred compositions according to the invention

A) at least 56% by weight, preferably at least 60% by weight of aromatic polycarbonate,

B) 10% to 35% by weight of one or more oxides of metals or metalloids of the third, fourth, and/or fourth transition group,

C) 0.2% to 6% by weight of PMMI copolymer and

D) optionally additional additives

It contains.

Also more preferred compositions according to the invention are

A) at least 60% by weight of aromatic polycarbonate,

B) from 10% to 30% by weight of one or more oxides of metals or metalloids of the third, fourth, and/or fourth transition group,

C) 0.2% to 6% by weight of PMMI copolymer and

D) optionally selected from the group consisting of flame retardants, anti-dropping agents, impact modifiers, fillers, antistatic agents, colorants, pigments, carbon black, lubricants and/or release agents, heat stabilizers, compatibilizers, UV absorbers and/or IR absorbers, One or more additional additives separate from components B and C

It contains.

A) at least 68% by weight of aromatic polycarbonate,

B) up to 20% by weight (ie, including 20% by weight) of one or more oxides of metals or metalloids of the third, fourth, and/or fourth transition group,

C) 1% to 3% by weight of PMMI copolymer and

D) optionally selected from the group consisting of flame retardants, anti-dropping agents, impact modifiers, fillers, antistatic agents, colorants, pigments, carbon black, lubricants and/or release agents, heat stabilizers, compatibilizers, UV absorbers and/or IR absorbers, One or more additional additives separate from components B and C

The composition consisting of is particularly preferred.

This composition has excellent mechanical performance and excellent heat resistance.

Very particularly preferred compositions according to the invention

A) at least 68% by weight of aromatic polycarbonate,

B) from 15% to 25% by weight of one or more oxides of metals or metalloids of the third, fourth, and/or fourth transition group,

C) 1.5% to 6% by weight, especially 4% to 6% by weight of PMMI copolymer and

D) optionally up to 10.0% by weight of flame retardants, anti-dropping agents, impact modifiers, fillers separate from component B, antistatic agents, colorants, pigments, carbon black, lubricants and/or release agents, heat stabilizers, compatibilizers, UV One or more additional additives separate from components B and C, selected from the group consisting of absorbents and/or IR absorbers

Is made of

In embodiments described as preferred, the proportion of methylmethacrylimide units in the PMMI copolymer, in each case based on the total weight of the PMMI copolymer present in the composition, is at least 30% by weight, and methyl methacrylate units The proportion of 3 to 65% by weight, the proportion of methyl methacrylic acid and methyl methacrylic anhydride unit is less than 15% by weight in total, the acid value measured according to DIN 53240-1:2013-06 is 15 to 50 Particular preference is given to mg KOH/g, very particularly preferably from 20 to 45 mg KOH/g.

The production of the polymer composition according to the invention containing mixed components A), B), C) and optionally D) and optionally further components can be carried out using a powder pre-mix. It is also possible to use additives according to the invention and powders and pre-mixtures of pellets or pellets. It is also possible to use a premix produced from a solution of the mixing component in a suitable solvent, where homogenization is optionally carried out in solution, followed by removal of the solvent. In particular, the additives referred to as component D of the composition according to the invention and also further components can be introduced by known methods or in the form of a masterbatch. The use of a masterbatch is particularly preferred for the introduction of additives and additional components, in particular a masterbatch based on each polymer matrix is used.

The composition according to the invention can be extruded, for example. After extrusion, the extrudate can be cooled and ground. The mixing and mixing of the premix in the melt can also be carried out in a plasticizing unit of an injection molding machine. In this case, the melt is converted directly into a molded article in a subsequent step.

In particular, the composition according to the invention has been found to be particularly suitable for the production of extrudates, preferably for extrusion of profiles and sheets.

Home appliances (vacuum cleaners, air conditioning units, shavers, etc.) as housing materials in the electrical/electronics field, for example for electric instruments, mobile electronic devices (mobile phones, laptops, tablets, etc.), and also for TV housings. It is also possible to use a composition for the purpose, in particular as a housing material.

Since SiO ₂ and Al ₂ O ₃ exhibit, for example, certain thermal conductivity and introduce them into plastic articles, the field of heatsink is a further application for the composition according to the invention.

The compositions according to the invention are also suitable for applications requiring high surface quality and/or high dimensional stability, for example printed circuit boards or reflectors in the electronics field. In these applications where a low coefficient of thermal expansion is essential, a large amount of filler is used, and good stabilization is particularly important.

In the polycarbonate composition, which is required to have high reflectivity, that is, the reflective white type, titanium dioxide is used. Such compositions find use in, for example, optical applications, as background materials for displays, for example, or in optical fiber or LED systems, such as, for example, in smartphones. The composition according to the invention is also suitable as a matrix material for complex formation. Composites are understood to mean composite materials made of matrix materials and inorganic fiber materials, in particular glass fibers, carbon fibers, and the like.

Stabilization of the polycarbonate composition with a PMMI copolymer is particularly preferred in the presence of high residence times, ie residence times up to several minutes, ie in co-kneaders, for example.

Example:

polymer:

PC1: MVR of 19 cm 3/10 min (300° C./1.2 kg, ISO 1133-1:2011) and Vicat at 145° C. Commercially available polycarbonate based on bisphenol A, with softening temperature (VST/B 120; ISO 306:2013) (Makrolon® 2408 from Covestro Deutschland AG). M _w measured as described below, about 23,900 g/mol.

PC2: based on bisphenol A and bisphenol TMC, with an MVR of 18 cm 3/10 min (330° C./2.16 kg, ISO 1133-1:2011) and a softening temperature of 183° C. (VST/B 120; ISO 306:2013) Commercially available copolycarbonate (Apec® 1895 from Covestro Deutschland AG). M _w measured as described below, about 27,900 g/mol.

Stabilizer:

PMMI1: Polymethylmethacrylimide copolymer from Evonik ( fleximide® 8803) with a softening temperature of 130° C. (VST/B 50; ISO 306:2013). Acid value: 22.5 mg KOH/g, measured according to DIN 53240-1:2013-06. Proportion of MMI (methylmethacrylimide): 36.8 wt%, proportion of MMA (methyl methacrylate): 51.7 wt%, proportion of MMS (methylmethacrylic acid) + MMAH (methylmethacrylic anhydride): 11.5 weight %, based on the total weight of PMMI in each case, determined by quantitative ¹ H-NMR spectroscopy.

PMMI2: Polymethylmethacrylimide copolymer (Pleximide® TT50) from Evonik with a softening temperature of 150°C (VST/B 50; ISO 306:2013). Acid value: 22.5 mg KOH/g, measured according to DIN 53240-1:2013-06. Ratio of MMI: 83.1% by weight, ratio of MMA: 13.6% by weight, ratio of MMS + MMAH: 3.3% by weight, based on the total weight of PMMI in each case, measured by quantitative ¹ H NMR spectroscopy.

PMMI3: Polymethylmethacrylimide copolymer (Pleximide® TT70) from Evonik with a softening temperature of 170°C (VST/B 50; ISO 306:2013). Acid value: 41.5 mg KOH/g, measured according to DIN 53240-1:2013-06. Ratio of MMI: 94.8% by weight, Ratio of MMA: 4.6% by weight, Ratio of MMS + MMAH: 0.6% by weight, based on the total weight of PMMI in each case, determined by quantitative ¹ H NMR spectroscopy.

Stab1: M _w = 6301 g/mol, M _n = 1159 g/mol with an average molecular weight (gel permeation chromatography in ortho-dichlorobenzene at 150°C under polystyrene correction), acid value of 52.6 mg KOH/g (test Maleic anhydride-modified ethylene-propylene-1-octene terpolymer wax from Mitsui Chemical America, Inc. with method JIS K0070 (ethene:propene:1-octene) Weight ratio 87:6:7) (High Wax ^TM 1105A). Maleic anhydride content: 4.4% by weight, based on the total weight of the terpolymer.

Stab2: M _w = 20,700 g/mol, M _n = 1460 g/mol with an average molecular weight (gel permeation chromatography in ortho-dichlorobenzene at 150° C. under polystyrene correction) and an acid value of 78 mg KOH/g (ASTM D-1386) maleic anhydride-modified polypropylene copolymer (AC907P) from Honeywell.

Filler:

F1: Titanium dioxide from chronos with D ₅₀ =210 nm (scanning electron microscopy, ECD method; Kronos® 2230).

F2: Quartz material (D ₅₀ = 4 μm, D ₉₈ = 13 μm, not sized) from Quarzwerke GmbH (50226 Frechen, Germany) available under the trade name Amosil FW600. It is calcined silicon dioxide with a D ₁₀ /D ₉₀ ratio of about 1.5/10 measured according to ISO 13320:2009 and a specific surface area of about 6 m 2 /g measured according to DIN-ISO 9277:2014-01.

F3: Aluminum oxide from Fluka, measured at room temperature with a Mettler Toledo MP230 pH meter and also according to ISO 10390:2005 in aqueous suspension, with a pH of 7.2.

Generating parameters :

Method A ^[One] :

The extruder used was a DSM micro-extruder MIDI 2000 with a capacity of 15 cm 3. The melt temperature in the extruder was 280°C, the speed was 150 rpm, and the residence time (RT) was 5 or 10 minutes. DSM injection molding machines were used in injection molding. During injection molding, the melt temperature was 300°C and the mold temperature was 80°C.

Method B ^[2] :

The extruder used was a KraussMaffei Berstorff ZE 25 AX 40D-UTX twin-screw extruder. The melt temperature in the extruder was 300° C., the speed was 100 rpm, and the throughput was 10 kg/h. The torque was 15% to 40%. Filler addition was performed in housing 5 (out of 9) through a side extruder.

Analysis method:

M _w : Gel permeation chromatography corrected for bisphenol A polycarbonate standard using dichloromethane as eluent. Calibrated using a linear polycarbonate (formed from bisphenol A and phosgene) with a known molar mass distribution from PS Polymers Standards Services Geembeha (Germany), Kurenta Geembehaunt Co. Correction by method 2301-0257502-09D (2009, German) from Oheh (Leverkusen, Germany). The eluent is dichloromethane. Column combination of crosslinked styrene-divinylbenzene resin. Diameter of the analytical column: 7.5 mm; Length: 300 mm. The particle size of the column material: 3 μm to 20 μm. Concentration of solution: 0.2% by weight. Flow rate: 1.0 ml/min, solution temperature: 30°C. Injection volume: 100 μl. Detection by UV detector.

The yellowing index (YI) was measured according to ASTM E313-10. The transmission value (Ty) was measured according to ASTM-E-308, and the reflectance was measured according to ASTM E 1331. Both YI and Ty and reflectance Ry were evaluated according to D65, 10° (light type: D65/observer: 10°). Gloss was measured according to ASTM D 523 Hunter UltraScanPRO, diffusion/8° (reference: absolute ceramic value). Color values (L*a*b) were measured according to DIN EN ISO 11664-4:2012-06. The sample had a geometry of 6.0 mm x 3.5 mm x 1.5 mm.

The viscosity of the polymer melt was measured according to ISO 11443:2005 at a melt temperature of 300° C. and a shear rate of 1000 s ⁻¹ .

The Vicat softening temperature (VST/B/50) of the composition was measured on a test piece according to ISO 306:2013.

The tensile modulus and tensile strength of the composition were measured on a test piece according to ISO 527-1:2012.

The penetration force and penetration deformation of the composition were measured on a test piece according to ISO 6603-2:2000.

result:

Example:

Table 1: Filler-free polycarbonate ^[One] And effects of PMMI

[1] The composition produced by method A

In unfilled polycarbonate, there is no significant degradation of the polymer chain. Therefore, no stabilizer is required. As is evident from Table 1, the addition of PMMI to the filler-free polycarbonate does not have any adverse effect on molecular weight. The average molecular weight is at a constant level within the measurement accuracy range.

Table 2: Filler-free polycarbonate ^[One] And effects of PMMI

[1] The composition produced by method B

In unfilled polycarbonate, the three types of PMMI used exhibit substantially the same characteristics. Addition of 1% by weight of PMMI copolymer has only minimal effect on Vicat temperature. However, the effect of different softening temperatures of various PMMI copolymer types is already evident at 1% by weight addition:

Table 3: Titanium dioxide-containing polycarbonate composition ^[One] Effects of PMMI copolymer

[1] The composition produced by method B

An additional 20% by weight of titanium dioxide results in molecular weight degradation of the polycarbonate, which is remarkable (up to 21,300 g/mol) compared to pure polycarbonate. A small amount of PMMI copolymer of 0.2% by weight also provides a marked reduction in molecular weight degradation. The addition of only 2% by weight of the PMMI copolymer already provides the attainment of a planar range, where further addition of PMMI no longer has a notable effect, and the molecular weight of the polycarbonate is the molecular weight of the pure polycarbonate. Than just a little less. Even after a residence time of 5 minutes, the molecular weight is still at the level of the unfilled polycarbonate.

For yellowing (Y.I.), no significant difference is apparent within the concentration range (0 wt% to 6 wt% PMMI copolymer); When present, a tendency to minimal yellowing is seen. The L-value did not change compared to the unstabilized composition (Example 11V), and the reflectivity Ry of the titanium dioxide-filled polycarbonate was not affected by the addition of the PMMI copolymer.

Table 4: Titanium dioxide-containing polycarbonate composition ^[One] And the effects of different PMMI types

[1] The composition produced by method A

The type of PMMI copolymer used differs in its MMI, MMA, acid and anhydride content. There is no detectable related difference in stabilization of the titanium dioxide-filled polycarbonate composition between different PMMI copolymers. Each of the three PMMI copolymers provides excellent stabilization. Even for yellowing, there is no significant difference detectable. Compared to the non-added polycarbonate composition (Example 18V), the addition of PMMI copolymer was Y.I. It provides a slight reduction in the value and thus an improvement in yellowing.

Table 5: Comparison of different acid/maleic anhydride-functionalized copolymers as stabilizers ^[One]

[1] The composition produced by method A

When combined with titanium dioxide as filler, PMMI1, Stab 1 and Stab 2 provide approximately equally effective stabilization of polycarbonate.

In unfilled polycarbonates (Examples 22V to 24V), the addition of PMMI copolymers was significantly reduced compared to polycarbonates containing stabilizers Stab1 and Stab 2 Y.I. Provide a value (ie lower yellowing). Compared to PMMI copolymers, Stab1 and Stab 2 result in more intense turbidity, which is detectable by a 61%/48% reduction in permeation.

Table 6: Different filler/additive ratios ^[One]

[1] The composition produced by method A

Titanium dioxide-filled PCs have maximum achievable stabilization limits at 10% to 30% by weight filler. It is approximately 23000-23500 g/mol. In PMMI copolymers greater than about 0.5% by weight, the molecular weight no longer significantly changes.

Table 7: Titanium dioxide-filled (co)polycarbonate compositions using various PMMI copolymer types and waxes ^[One] Stabilization of.

[1] The composition produced by method B

PMMI copolymer types 2 and 3 provide a significantly poor elongation at break, i.e. toughness, compared to PMMI copolymer I in bicarbonate based on bisphenol A (see Examples 52, 53 and 43), but nonetheless this is an excellent range Within. In the polycarbonate copolymer PC-2 as base material, there is no noticeable difference in the elongation at breakable detectable between the types of PMMI copolymers used (Examples 55 to 57). However, even at a 1% by weight PMMI copolymer, a clear effect on molecular weight stabilization is detectable, which is likely to be even more pronounced for higher amounts of PMMI copolymer. Compared to the non-added composition (Ex. 54V), addition of only 1% by weight of PMMI1 in PC-2 also provides markedly improved impact characteristics and increased elongation at break (Ex. 55). In PC-2, all three PMMI copolymer types increase toughness while maintaining strength/rigidity unchanged (see Ex. 54 V and Ex. 55-57).

Stabilization with Stab1 and Stab2 in the same amount (1% or 2% by weight) for PMMI copolymer 1 for comparison has a similar effect on reducing molecular weight degradation. However, compositions containing the polyolefin system Stab1/Stab2 show a related decrease in Vicat temperature. Additionally, the mechanical properties are entirely poor compared to compositions comprising PMMI copolymers; Tensile modulus and tensile strength are reduced. The addition of Stab1 and Stab2 also results in significantly poorer impact characteristics (measured by the maximum force achievable in the penetration test) compared to the addition of PMMI1 (compare Ex. 46V-49V and Ex. 43, 44).

Table 8: Calcined silicon dioxide-containing polycarbonate composition ^[One] And effects of PMMI copolymer

[1] The composition produced by method A

Compared to other inorganic fillers, the calcined silicon dioxide used herein has better compatibility with polycarbonates, as is apparent from lower molecular weight degradation of only about 1000 g/mol without additional stabilizers. The slightly acidic nature of silicon dioxide has less pronounced incompatibility with polycarbonate. However, here also a stabilizing effect can also be achieved by the addition of the PMMI copolymer, and the plateau range is achieved before about 2% by weight. Higher concentrations of 4-6% do not provide further improvement.

Especially at higher residence times of 10 minutes, this stabilization is still effective and the molecular weight is at the level of unfilled PC. Without the PMMI copolymer the molecular weight is reduced by an additional 1000 g/mol (Example 58V), but the molecular weight of the added compound (Examples 62-64) remains unchanged.

Table 9: Measurement of material properties for stabilized compounds ^[One]

[1] The composition produced by method B; [2] Sample too thin

Upon addition of the wax Stab1, the tensile modulus is slightly reduced (Examples 74V, 75V) compared to the PMMI copolymer added composition (Examples 71, 72). The tensile strength remains approximately constant or slightly increases with the addition of the PMMI copolymer (Examples 69 to 73), but decreases markedly with the addition of Stab1 or Stab2. The filler itself initially has a reinforcing effect, but it is partially lost again (even though they have a stabilizing effect) due to Stab1 or Stab2; Stab1 and Stab2 have a plasticizing effect. Vicat temperatures also decrease significantly (Ex. 71, 72 and 74V-77V). PMMI copolymers also provide slightly better stabilization compared to Stab1 and Stab2 (Ex. 71, 72 and 74V-77V). A plateau range is achieved after an amount of about 1% by weight added.

Compositions containing 10% by weight of calcined silicon dioxide and PMMI copolymers (Examples 65-67) show very high elongation at break values.

Table 10: Calcined silicon dioxide-containing polycarbonate composition ^[One] And the effects of different PMMI types

[1] The composition produced by method B

Examples 83-85 show that the PMMI copolymer (PMMI1) with the lowest imide ratio in the silicon dioxide-containing composition has the strongest stabilizing effect against molecular weight degradation. PMMI2 achieves the best fluidity, ie the best mechanical properties (tensile, penetrating) combined with the lowest viscosity and the best Vicat temperature.

Table 11: Aluminum oxide-filled composition ^[One] And effects of PMMI copolymer

[1] The composition produced by method A

The degradation caused by 10% by weight of Al ₂ O ₃ at a residence time of 5 min is already very significant, but can only be significantly reduced when using only 1% PMMI copolymer.

Claims (15)

At least one PMMI for reducing molecular weight degradation of aromatic polycarbonates in a polycarbonate composition containing one or more oxides of metals or metalloids of the third, fourth, and/or fourth transition group during blending Use of the copolymer. The method of claim 1, wherein the PMMI copolymer, based on the total weight of the PMMI copolymer in each case, 3% to 65% by weight of methyl methacrylate units, at least 30% by weight of methyl methacrylimide units , 15% by weight or less of methyl methacrylic acid units and methyl methacrylic anhydride units, and 15 to 50 　mg　KOH/g of acid value measured according to DIN 53240-1:2013-06. A) aromatic polycarbonate,
B) one or more oxides of metals or metalloids of the third, fourth and/or fourth transition group,
C) PMMI copolymer and
D) optionally additional additives
The composition containing. According to claim 3,
A) at least 55% by weight of aromatic polycarbonate,
B) from 5% to 44% by weight of one or more oxides of metals or metalloids of the third, fourth, and/or fourth transition group,
C) 0.1% to 8% by weight of PMMI copolymer and
D) optionally additional additives
The composition containing. The method of claim 3 or 4,
A) at least 56% by weight of aromatic polycarbonate,
B) 10% to 35% by weight of one or more oxides of metals or metalloids of the third, fourth, and/or fourth transition group,
C) 0.2% to 6% by weight of PMMI copolymer and
D) optionally additional additives
The composition containing. The method according to any one of claims 3 to 5,
A) at least 60% by weight of aromatic polycarbonate,
B) 10% to 30% by weight of one or more oxides of a third or fourth main group or fourth transition group metal or metalloid,
C) 0.2% to 6% by weight of PMMI copolymer and
D) Optionally, a group consisting of flame retardants, anti-dropping agents, impact modifiers, fillers, antistatic agents, colorants, pigments, carbon black, lubricants and/or release agents, heat stabilizers, blend partners, compatibilizers, UV absorbers and/or IR absorbers One or more additional additives separate from components B and C, selected from
The composition consisting of. The composition according to any of claims 3 to 6, containing at least 1.5% by weight of the PMMI copolymer, based on the total composition. The at least one oxide and at least 1.0% by weight of at least one of the metals or metalloids of any of the third, fourth and/or fourth transition groups of 15 to 25% by weight. A composition containing a PMMI copolymer. The composition or agent according to any one of claims 3 to 8, wherein the PMMI copolymer has a methyl methacrylate unit, a methyl methacrylimide unit, a methyl methacrylic acid unit, and a methyl methacrylic anhydride unit. Use according to paragraph 1. Based on the total weight of the PMMI copolymer present in the composition in each case, the proportion of methyl methacrylimide units is at least 30% by weight, and the proportion of methyl methacrylate units is 3% to 65% by weight, The composition according to any one of claims 3 to 9 or the use according to claim 1 or 9, wherein the proportion of methylmethacrylic acid and methylmethacrylic anhydride unit is 15% by weight or less in total. The composition according to any one of claims 3 to 10 or 1, 9 and 9, wherein the acid value of the PMMI copolymer measured according to DIN 53240-1:2013-06 is 15 to 50　mg　KOH/g. Use according to claim 10. The proportion of the oxides of the metals or metalloids of the third, fourth and/or fourth transition groups is 15% to 25% by weight, based on the total composition, and the third group relative to the PMMI copolymer, The composition according to any one of claims 3 to 11, wherein the ratio of the oxides of the metals or metalloids of the fourth main group and/or the fourth transition group is 40 or less. And use according to claim 11. The composition according to any one of claims 3 to 12 or any one of claims 1 to 9 to 12, wherein the proportion of the PMMI copolymer in the finished composition is 2% by weight to 6% by weight. Use according to. A molded article made from the composition according to claim 3 or comprising an area thereof. 15. The molded article of claim 14, wherein the profile in the electrical/electronics field, plate, housing part, printed circuit board in the electronics field, heatsinks, reflectors, elements for optical applications, composites.